CN111484020A - Tail-free utilization method of high-magnesium phosphate tailings - Google Patents
Tail-free utilization method of high-magnesium phosphate tailings Download PDFInfo
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- CN111484020A CN111484020A CN202010310982.XA CN202010310982A CN111484020A CN 111484020 A CN111484020 A CN 111484020A CN 202010310982 A CN202010310982 A CN 202010310982A CN 111484020 A CN111484020 A CN 111484020A
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- magnesium
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- tailings
- phosphorus
- filtrate
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- 239000004137 magnesium phosphate Substances 0.000 title claims abstract description 38
- 229960002261 magnesium phosphate Drugs 0.000 title claims abstract description 38
- 229910000157 magnesium phosphate Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 118
- 239000000706 filtrate Substances 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011574 phosphorus Substances 0.000 claims abstract description 64
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 64
- 239000011777 magnesium Substances 0.000 claims abstract description 49
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011575 calcium Substances 0.000 claims abstract description 39
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012716 precipitator Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 10
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 10
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 8
- 239000010440 gypsum Substances 0.000 claims abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 60
- 238000001354 calcination Methods 0.000 claims description 32
- 238000000967 suction filtration Methods 0.000 claims description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 27
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 9
- 239000010452 phosphate Substances 0.000 abstract description 9
- 239000010453 quartz Substances 0.000 abstract description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 4
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 hydrogen halides Chemical class 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- INIZPXBLAMXMBJ-UHFFFAOYSA-O azanium;magnesium;nitrate Chemical compound [NH4+].[Mg].[O-][N+]([O-])=O INIZPXBLAMXMBJ-UHFFFAOYSA-O 0.000 description 1
- BJPSZEJAKKDDCT-UHFFFAOYSA-L calcium;chloro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(Cl)=O BJPSZEJAKKDDCT-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/20—Magnesium hydroxide by precipitation from solutions of magnesium salts with ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a tailings tailless utilization method of high-magnesium phosphate tailings, which comprises the steps of firstly carrying out acidolysis on the phosphate tailings, treating silicon slag obtained by acidolysis to convert the silicon slag into silicon dioxide, mixing acidolysis solution with an acid precipitator, carrying out calcium precipitation reaction to obtain gypsum powder and calcium precipitation filtrate, then adding an alkali precipitator into the calcium precipitation filtrate, carrying out phosphorus precipitation reaction to obtain magnesium ammonium phosphate and phosphorus precipitation filtrate, then concentrating the phosphorus precipitation filtrate to obtain ammonium chloride and ammonium precipitation filtrate, and finally adding a precipitator into the ammonium precipitation filtrate, carrying out magnesium precipitation reaction to obtain magnesium carbonate and magnesium precipitation filtrate. The invention comprehensively utilizes calcium, magnesium, phosphorus and silicon elements in the phosphate tailings, converts calcium in the tailings into calcium sulfate whisker products, converts magnesium into magnesium carbonate or magnesium hydroxide products, converts phosphorus into magnesium ammonium phosphate products, and converts quartz which is difficult to treat in the tailings into superfine silicon dioxide products, thereby achieving tailless utilization of the tailings and providing a new way for comprehensive utilization of the tailings.
Description
Technical Field
The invention relates to the technical field of waste resource utilization, in particular to a high-magnesium phosphate tailing tailless utilization method.
Background
The high-magnesium phosphate tailings are industrial wastes, mainly come from tailings slag left after ore dressing to extract concentrate, and belong to mining solid wastes among the industrial solid wastes according to subdivision. At present, the treatment and utilization status of high-magnesium phosphate tailings is severe, phosphate tailings which cannot be effectively treated for a long time are accumulated like a mountain, serious pollution is caused to the environment, and the waste of resources is caused, so the treatment of the phosphate tailings is an important subject facing the research of the phosphorus chemical industry at present.
The main phases of the high-magnesium phosphate tailings are dolomite, fluorapatite and quartz. Wherein the main available elements are calcium, magnesium, phosphorus and silicon. Most of the prior high-magnesium phosphate tailings are treated in an acid-soluble mode, but the method only can utilize calcium, magnesium and phosphorus elements which are soluble in acid in the tailings, and the relatively stable quartz becomes waste in the tailings utilization process because the quartz cannot be dissolved in the acid. Therefore, the utilization of quartz in tailings is an urgent problem to be solved.
Silica, which is a raw material for manufacturing glass, quartz glass, water glass, optical fiber, important parts of the electronic industry, optical instruments, handicrafts, and refractory materials, is an important material for scientific research. However, silica is chemically stable, insoluble in water and unreactive with water, is an acidic oxide, unreactive with general acids, and inactive, and does not react with halogens other than fluorine and hydrogen fluoride, hydrogen halides, and sulfuric acid, nitric acid, perchloric acid (except hot concentrated phosphoric acid).
Silica is one of the most important high-tech superfine inorganic new materials, and has the unique properties of large specific surface area, strong surface adsorption, large surface energy, high chemical purity, good dispersibility, thermal resistance, electrical resistance and the like due to small particle size, and has the unique characteristics of excellent stability, reinforcement, thickening property and thixotropy in various subjects and fields, so that the silica has an irreplaceable effect. The fumed silica is commonly called ultra-fine white carbon black, is widely used in various industries as an additive, a catalyst carrier, a petrochemical industry, a decolorizing agent, a flatting agent, a rubber reinforcing agent, a plastic filling agent, an ink thickening agent, a metal soft polishing agent, an insulating and heat-insulating filling agent, an advanced daily cosmetic filling material, a spraying material, medicine, environmental protection and other fields, and provides a new material basis and technical guarantee for the development of related industrial fields. It is greatly regarded as showing a specific function in the aspects of magnetism, catalysis, light absorption, thermal resistance, melting point and the like as compared with the conventional materials.
In the prior art, some patents relate to the comprehensive utilization of high-magnesium phosphate tailings, and Chinese patent with publication number CN 110510652A discloses a comprehensive utilization method of high-magnesium phosphate tailings, which converts phosphorus in the high-magnesium phosphate tailings into calcium chlorophosphate, converts calcium and magnesium into calcium sulfate and magnesium hydroxide products, has simple flow and convenient operation, but does not utilize quartz slag after acid dissolution; the Chinese patent with publication number CN 108975985A discloses a comprehensive utilization method of high-magnesium phosphorus tailings, which converts calcium in the tailings into calcium sulfate products and converts magnesium and phosphorus into compound fertilizers, thereby improving the added value of the tailings and not relating to the utilization of silicon in the tailings; chinese patent publication No. CN 110451473 a discloses a comprehensive utilization method of high magnesium phosphate tailings by cyclic acid leaching, which separates silicon slag from the high magnesium phosphate tailings by hydrochloric acid acidolysis, and prepares products such as calcium sulfate, magnesium hydroxide and the like by using acidolysis solution, while the silicon slag is not utilized; chinese patent publication No. CN 104860287 a discloses a method for preparing magnesium ammonium phosphate and magnesium ammonium nitrate from phosphate tailings, in which phosphate tailings are decomposed with nitric acid, decalcification is performed with ammonium sulfate, and ammonia water is added to the decalcification solution to prepare magnesium ammonium phosphate fertilizer, and also silicon resources in the tailings are not utilized.
Disclosure of Invention
In view of the above, the invention aims to provide a high-magnesium phosphate tailing tailless utilization method to solve the problems of low resource utilization rate and low product added value of the existing phosphate tailings.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high-magnesium phosphate tailing tailless utilization method comprises the following steps:
1) mixing the high-magnesium phosphate tailings with industrial hydrochloric acid, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and suction filtration to obtain acidolysis solution and silicon slag.
2) Mixing the silicon slag with anhydrous sodium carbonate, and calcining to obtain sodium silicate;
3) dissolving the sodium silicate in distilled water, adding a surfactant, stirring, adding hydrochloric acid, aging, filtering, washing, drying and calcining to obtain silicon dioxide;
4) mixing the acidolysis solution with an acid precipitator, performing calcium precipitation reaction, and after the calcium precipitation reaction is finished, performing suction filtration to obtain gypsum powder and calcium precipitation filtrate;
5) adding an alkali precipitator into the calcium precipitation filtrate to perform a phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, performing suction filtration to obtain magnesium ammonium phosphate and a phosphorus precipitation filtrate;
6) concentrating and filtering the phosphorus precipitation filtrate to obtain ammonium chloride and an ammonium precipitation filtrate;
7) and adding a precipitator into the ammonium precipitation filtrate to perform magnesium precipitation reaction, and after the magnesium precipitation reaction is finished, performing suction filtration to obtain magnesium carbonate and magnesium precipitation filtrate.
Optionally, the tailless utilization method of the high-magnesium phosphate tailings further includes the following steps: and merging the magnesium-precipitation filtrate into the next calcium-precipitation filtrate for phosphorus-precipitation reaction.
Optionally, the concentration of the hydrochloric acid in the step 1) is 8.80-12.07 mol/L, and the mass ratio of the hydrochloric acid to the high-magnesium phosphate tailings is 1.5-2.25: 1.
Optionally, the reaction temperature of the acidolysis reaction in the step 1) is 20-60 ℃, and the reaction time is 20-60 min; the suction filtration temperature of the heat preservation suction filtration in the step 1) is 20-60 ℃.
Optionally, the addition amount of the anhydrous sodium carbonate in the step 2) is 1-2 times of the mass of the silicon slag; the calcination temperature in the step 2) is 500-1000 ℃, and the calcination time is 10-80 min.
Optionally, the surfactant in step 3) is PEG-2000, or is cetyltrimethylammonium bromide.
Optionally, the aging time of the aging in the step 3) is 1-5 h; the calcination temperature in the step 3) is 300-600 ℃, and the calcination time is 1-4 h.
Optionally, the acid precipitating agent in step 4) is sulfuric acid, or is ammonium sulfate; the alkali precipitator in the step 5) is ammonia water or ammonia gas.
Optionally, the step 6) of concentrating the phosphorus precipitation filtrate comprises: and concentrating the phosphorus precipitation filtrate to 50-80% of the original volume.
Optionally, in the step 7), the precipitant is one of ammonium carbonate, sodium hydroxide, ammonia water and potassium hydroxide.
Compared with the prior art, the high-magnesium phosphate tailing tailless utilization method has the following advantages:
1. the invention comprehensively utilizes calcium, magnesium, phosphorus and silicon elements in the phosphate tailings, converts calcium in the tailings into calcium sulfate whisker products, converts magnesium into magnesium carbonate or magnesium hydroxide products, converts phosphorus into magnesium ammonium phosphate products, converts quartz which is difficult to treat in the tailings into superfine silicon dioxide products, comprehensively utilizes all major elements in the phosphate tailings, achieves tailless utilization of the tailings, increases the added value of the tailings, and provides a new way for comprehensive utilization of the tailings.
2. The phosphorus tailings and the industrial hydrochloric acid used in the invention both belong to industrial wastes, so that the resource utilization cost is low, the process is simple, the operation is convenient, theoretical support is provided for comprehensive utilization of the phosphorus tailings and further industrialization, and theoretical basis is provided for burden reduction and income increase of enterprises.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a process flow diagram of the high-magnesium phosphate tailing tailless utilization method of the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
With reference to fig. 1, the method for tailless utilization of high-magnesium phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 210m L mass percent 29% (10.18 mol/L) of industrial hydrochloric acid, placing the industrial hydrochloric acid in a clean three-neck flask, weighing 100g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing at 55 ℃ for 20min, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and filtration at 60 ℃ to obtain acidolysis solution and silicon slag;
2) placing the obtained silicon slag in a crucible, adding 15g of anhydrous sodium carbonate, uniformly mixing, placing in a muffle furnace, calcining at 750 ℃ for 60min, and naturally cooling after calcining to obtain a calcined product, namely sodium silicate solid;
3) dissolving the obtained sodium silicate with 50ml of distilled water, adding 5g of PEG-2000 (polyethylene glycol-2000), stirring, slowly dropwise adding analytic hydrochloric acid to adjust the pH value of the solution to 5.5, aging for 2 hours after the dropwise adding of the hydrochloric acid is finished, then, filtering, washing, drying, then, putting into a muffle furnace, calcining for 1.5 hours at 400 ℃, and naturally cooling after the calcining is finished to obtain an ultrafine silicon dioxide product;
4) dripping 50ml of 98% sulfuric acid into the acidolysis solution obtained in the step 1), heating to 103 ℃, carrying out calcium precipitation reaction for a period of time, and carrying out suction filtration to obtain α -gypsum powder and calcium precipitation filtrate;
5) placing the calcium precipitation filtrate obtained in the step 4) into a 1000ml three-neck flask, slowly dropwise adding a certain amount of 25% ammonia water solution to adjust the pH value of the calcium precipitation filtrate to 5, carrying out phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, carrying out suction filtration to obtain a magnesium ammonium phosphate product and a phosphorus precipitation filtrate;
6) placing the filtrate of the phosphorus precipitation in a rotary evaporator for concentration until the volume of the filtrate is 70% of the volume of the original solution, and performing suction filtration to obtain ammonium chloride and filtrate of the ammonium precipitation;
7) putting the ammonium precipitation filtrate into a 1000ml three-neck flask, slowly adding a certain amount of ammonium carbonate, performing magnesium precipitation reaction, and obtaining magnesium carbonate solid and magnesium precipitation filtrate after the magnesium precipitation reaction is finished, wherein the magnesium precipitation filtrate is stored for the next phosphorus precipitation reaction, and the specific steps are as follows: and (4) merging the stored magnesium-separating filtrate into the next calcium-separating filtrate for the next phosphorus-separating reaction.
Example 2
With reference to fig. 1, the method for tailless utilization of high-magnesium phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 220m L mass percent 30.5% (10.28 mol/L) of industrial hydrochloric acid, placing the industrial hydrochloric acid in a clean three-neck flask, weighing 100g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 25min at 60 ℃, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and filtration at 60 ℃ to obtain acidolysis filtrate and silicon slag;
2) placing the obtained silicon slag in a crucible, adding 20g of anhydrous sodium carbonate, uniformly mixing, placing in a muffle furnace, calcining at 600 ℃ for 50min, and naturally cooling after calcining to obtain a calcined product, namely sodium silicate solid;
3) dissolving the obtained sodium silicate with 50ml of distilled water, adding 10g of PEG-2000 (polyethylene glycol-2000), stirring, slowly dropwise adding analytic hydrochloric acid to adjust the pH value of the solution to 6.0, aging for 3 hours after the dropwise adding of the hydrochloric acid is finished, then, filtering, washing, drying, then, putting into a muffle furnace, calcining for 1.5 hours at 450 ℃, and naturally cooling after the calcining is finished to obtain an ultrafine silicon dioxide product;
4) dropwise adding 110ml of ammonium sulfate solution into the acidolysis solution obtained in the step 1), heating to 105 ℃, carrying out calcium precipitation reaction for a period of time, and carrying out suction filtration to obtain α -gypsum powder and calcium precipitation filtrate;
5) placing the calcium precipitation filtrate obtained in the step 3) into a 1000ml three-neck flask, slowly dropwise adding a certain amount of 25% ammonia water solution to adjust the pH value of the calcium precipitation filtrate to 6, carrying out phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, carrying out suction filtration to obtain a magnesium ammonium phosphate product and a phosphorus precipitation filtrate;
6) and (3) placing the filtrate for separating the phosphorus in a rotary evaporator for concentration until the volume of the filtrate is 80% of the volume of the original solution, and performing suction filtration to obtain ammonium chloride and a filtrate for separating the ammonium.
7) Putting the ammonium precipitation filtrate into a 1000ml three-neck flask, slowly adding a certain amount of ammonium carbonate, performing magnesium precipitation reaction, and obtaining magnesium carbonate solid and magnesium precipitation filtrate after the magnesium precipitation reaction is finished, wherein the magnesium precipitation filtrate is stored for the next phosphorus precipitation reaction, and the specific steps are as follows: and (4) merging the stored magnesium-separating filtrate into the next calcium-separating filtrate for the next phosphorus-separating reaction.
Example 3
With reference to fig. 1, the method for tailless utilization of high-magnesium phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 200m L mass percent 33% (10.48 mol/L) of industrial hydrochloric acid, placing the industrial hydrochloric acid in a clean three-neck flask, weighing 100g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 30min at 40 ℃, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and filtration at 60 ℃ to obtain acidolysis filtrate and silicon slag;
2) placing the obtained silicon slag in a crucible, adding 25g of anhydrous sodium carbonate, uniformly mixing, placing in a muffle furnace, calcining at 800 ℃ for 30min, and naturally cooling after calcining to obtain a calcined product, namely sodium silicate solid;
3) dissolving the obtained sodium silicate with 50ml of distilled water, adding 12g of PEG-2000 (polyethylene glycol-2000), stirring, slowly dropwise adding analytic hydrochloric acid to adjust the pH value of the solution to 7.0, aging for 5 hours after the dropwise adding of the hydrochloric acid is finished, then, filtering, washing, drying, then, putting into a muffle furnace, calcining for 1.5 hours at 450 ℃, and naturally cooling after the calcining is finished to obtain an ultrafine silicon dioxide product;
4) dropwise adding 102ml of ammonium sulfate solution into the acidolysis solution obtained in the step 1), heating to 110 ℃, carrying out calcium precipitation reaction for a period of time, and carrying out suction filtration to obtain α -gypsum powder and calcium precipitation filtrate;
5) placing the calcium precipitation filtrate obtained in the step 3) into a 1000ml three-neck flask, slowly dropwise adding a certain amount of 25% ammonia water solution to adjust the pH value of the calcium precipitation filtrate to 6.5, carrying out phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, carrying out suction filtration to obtain an ammonium magnesium phosphate product and a phosphorus precipitation filtrate;
6) placing the filtrate of the phosphorus precipitation in a rotary evaporator for concentration until the volume of the filtrate is 65 percent of that of the original solution, and performing suction filtration to obtain ammonium chloride and filtrate of the ammonium precipitation;
7) putting the ammonium precipitation filtrate into a 1000ml three-neck flask, slowly adding a certain amount of ammonium carbonate, performing magnesium precipitation reaction, and obtaining magnesium carbonate solid and magnesium precipitation filtrate after the magnesium precipitation reaction is finished, wherein the magnesium precipitation filtrate is stored for the next phosphorus precipitation reaction, and the specific steps are as follows: and (4) merging the stored magnesium-separating filtrate into the next calcium-separating filtrate for the next phosphorus-separating reaction.
Example 4
With reference to fig. 1, the method for tailless utilization of high-magnesium phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 221m L mass percent 31.5% (10.21 mol/L) of industrial hydrochloric acid, placing the industrial hydrochloric acid in a clean three-neck flask, weighing 100g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 28min at 45 ℃, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and filtration at 60 ℃ to obtain acidolysis filtrate and silicon slag;
2) placing the obtained silicon slag in a crucible, adding 19g of anhydrous sodium carbonate, uniformly mixing, placing in a muffle furnace, calcining at 1000 ℃ for 10min, and naturally cooling after calcining to obtain a calcined product, namely a sodium silicate solid;
3) dissolving the obtained sodium silicate by using 50ml of distilled water, adding 10g of CTAB (cetyl trimethyl ammonium bromide), stirring, slowly dropwise adding an analytic hydrochloric acid to adjust the pH value of the solution to 7.5, aging for 4.5 hours after the hydrochloric acid is dropwise added, then, filtering, washing, drying, then, putting into a muffle furnace, calcining for 2 hours at 300 ℃, and naturally cooling to obtain an ultrafine silicon dioxide product after the calcination is finished;
4) dripping 55ml of 98% sulfuric acid into the acidolysis solution obtained in the step 1), heating to 105 ℃, performing calcium precipitation reaction for a period of time, and performing suction filtration to obtain α -gypsum powder and calcium precipitation filtrate;
5) placing the calcium precipitation filtrate obtained in the step 3) into a 1000ml three-neck flask, slowly dropwise adding a certain amount of 25% ammonia water solution to adjust the pH value of the calcium precipitation filtrate to 5.8, carrying out phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, carrying out suction filtration to obtain an ammonium magnesium phosphate product and a phosphorus precipitation filtrate;
6) placing the filtrate of the phosphorus precipitation in a rotary evaporator for concentration until the volume of the filtrate is 70% of the volume of the original solution, and performing suction filtration to obtain ammonium chloride and filtrate of the ammonium precipitation;
7) putting the ammonium precipitation filtrate into a 1000ml three-neck flask, slowly adding a certain amount of ammonium carbonate, performing magnesium precipitation reaction, and obtaining magnesium carbonate solid and magnesium precipitation filtrate after the magnesium precipitation reaction is finished, wherein the magnesium precipitation filtrate is stored for the next phosphorus precipitation reaction, and the specific steps are as follows: and (4) merging the stored magnesium-separating filtrate into the next calcium-separating filtrate for the next phosphorus-separating reaction.
Example 5
With reference to fig. 1, the method for tailless utilization of high-magnesium phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 198m L mass percent industrial hydrochloric acid with the mass fraction of 35.0% (10.79 mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 100g of high-magnesium phosphate tailing powder, gradually adding the high-magnesium phosphate tailing into the three-neck flask, after the high-magnesium phosphate tailing is added, opening condensed water, starting stirring, refluxing at 55 ℃ for 30min, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and filtration at 60 ℃ to obtain acidolysis filtrate and silicon slag;
2) placing the obtained silicon slag in a crucible, adding 20g of anhydrous sodium carbonate, uniformly mixing, placing in a muffle furnace, calcining at 900 ℃ for 20min, and naturally cooling after calcining to obtain a calcined product, namely sodium silicate solid;
3) dissolving the obtained sodium silicate by using 50ml of distilled water, adding 18g of CTAB (cetyl trimethyl ammonium bromide), stirring, slowly dropwise adding an analytic hydrochloric acid to adjust the pH value of the solution to 6.5, aging for 5 hours after the hydrochloric acid is dropwise added, then, filtering, washing, drying, then, putting into a muffle furnace, calcining for 1 hour at 600 ℃, and naturally cooling after the calcination is finished to obtain an ultrafine silicon dioxide product;
4) and (2) dropwise adding 52ml of 98% sulfuric acid into the acidolysis solution obtained in the step 1), heating to 106 ℃, performing calcium precipitation reaction for a period of time, and performing suction filtration to obtain α -gypsum powder and calcium precipitation filtrate.
5) Placing the calcium precipitation filtrate obtained in the step 3) into a 1000ml three-neck flask, slowly dropwise adding a certain amount of 25% ammonia water solution to adjust the pH value of the calcium precipitation filtrate to 7.0, carrying out phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, carrying out suction filtration to obtain an ammonium magnesium phosphate product and a phosphorus precipitation filtrate;
6) placing the filtrate of the phosphorus precipitation in a rotary evaporator for concentration until the volume of the filtrate is 66% of the volume of the original solution, and performing suction filtration to obtain ammonium chloride and filtrate of the ammonium precipitation;
7) putting the ammonium precipitation filtrate into a 1000ml three-neck flask, slowly adding a certain amount of ammonium carbonate, performing magnesium precipitation reaction, and obtaining magnesium carbonate solid and magnesium precipitation filtrate after the magnesium precipitation reaction is finished, wherein the magnesium precipitation filtrate is stored for the next phosphorus precipitation reaction, and the specific steps are as follows: and (4) merging the stored magnesium-separating filtrate into the next calcium-separating filtrate for the next phosphorus-separating reaction.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-magnesium phosphate tailing tailless utilization method is characterized by comprising the following steps of:
1) mixing the high-magnesium phosphate tailings with industrial hydrochloric acid, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out heat preservation and suction filtration to obtain acidolysis solution and silicon slag.
2) Mixing the silicon slag with anhydrous sodium carbonate, and calcining to obtain sodium silicate;
3) dissolving the sodium silicate in distilled water, adding a surfactant, stirring, adding hydrochloric acid, aging, filtering, washing, drying and calcining to obtain silicon dioxide;
4) mixing the acidolysis solution with an acid precipitator, performing calcium precipitation reaction, and after the calcium precipitation reaction is finished, performing suction filtration to obtain gypsum powder and calcium precipitation filtrate;
5) adding an alkali precipitator into the calcium precipitation filtrate to perform a phosphorus precipitation reaction, and after the phosphorus precipitation reaction is finished, performing suction filtration to obtain magnesium ammonium phosphate and a phosphorus precipitation filtrate;
6) concentrating and filtering the phosphorus precipitation filtrate to obtain ammonium chloride and an ammonium precipitation filtrate;
7) and adding a precipitator into the ammonium precipitation filtrate to perform magnesium precipitation reaction, and after the magnesium precipitation reaction is finished, performing suction filtration to obtain magnesium carbonate and magnesium precipitation filtrate.
2. The tailless utilization method of the high-magnesium phosphate tailings according to claim 1, further comprising the steps of: and merging the magnesium-precipitation filtrate into the next calcium-precipitation filtrate for phosphorus-precipitation reaction.
3. The tailless utilization method of the high-magnesium phosphate tailings according to claim 1, wherein the concentration of the hydrochloric acid in the step 1) is 8.80-12.07 mol/L, and the mass ratio of the hydrochloric acid to the high-magnesium phosphate tailings is 1.5-2.25: 1.
4. The tailings tailing-free utilization method of high magnesium phosphate according to claim 1, wherein the acidolysis reaction in the step 1) is carried out at a temperature of 20-60 ℃ for 20-60 min; the suction filtration temperature of the heat preservation suction filtration in the step 1) is 20-60 ℃.
5. The tailless utilization method of the high-magnesium phosphate tailings according to claim 1, wherein the addition amount of the anhydrous sodium carbonate in the step 2) is 1-2 times of the mass of the silica slag; the calcination temperature in the step 2) is 500-1000 ℃, and the calcination time is 10-80 min.
6. The tailless utilization method of the high-magnesium phosphate tailings of claim 1, wherein the surfactant in the step 3) is PEG-2000 or cetyl trimethylammonium bromide.
7. The tailless utilization method of the high-magnesium phosphate tailings according to claim 1, wherein the aging time of the aging in the step 3) is 1-5 h; the calcination temperature in the step 3) is 300-600 ℃, and the calcination time is 1-4 h.
8. The tailings without tail of high magnesium phosphorus according to claim 1, wherein the acid precipitator in step 4) is sulfuric acid, or ammonium sulfate; the alkali precipitator in the step 5) is ammonia water or ammonia gas.
9. The tailings without tailings of high magnesium phosphorus content of claim 1, wherein the step 6) of concentrating the phosphorus analysis filtrate comprises: and concentrating the phosphorus precipitation filtrate to 50-80% of the original volume.
10. The tailless utilization method of the high-magnesium phosphate tailings according to claim 1, wherein the precipitant in the step 7) is one of ammonium carbonate, sodium hydroxide, ammonia water and potassium hydroxide.
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| CN112675876A (en) * | 2020-12-25 | 2021-04-20 | 武汉工程大学 | Phosphorus tailings solid acid catalyst, preparation method thereof and application thereof in extracting saponin |
| CN116371386A (en) * | 2023-05-09 | 2023-07-04 | 北京神舟茂华环保科技有限公司 | Phosphate tailing-based magnetic mesoporous calcium silicate composite material and application thereof |
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